Tetrakisazo compounds

ABSTRACT

Compounds which in the form of the free acid correspond to the formula   WHEREIN R1, R2, n1, n2 and n3 have the meaning given in the description. The new dyestuffs dye vegetable and animal fibre materials and are particularly well suited for dyeing and printing of leather. They show good fastness properties, such as e.g., resistance to acid, resistance to alkalies, resistance to formaldehyde, resistance to solvents, resistance to fatliquoring, or dyeability in hard water; in particular the good fastness to light of the dyestuffs is to be stressed.

United States Patent [191 Goebel 1 1 Jan. 21, 1975 [54] TETRAKISAZOCOMPOUNDS [75] Inventor: Hermann GoebeLLeverkuscn,

Germany [73] Assigncc: Bayer Aktiengesellschaft,

Lcvcrkusen, Germany [221 Filed: Aug. 4, 1972 211 App]. No.: 278,089

[30] Foreign Application Priority Data Primary ExaminerLorraine A.Weinberger Assistant Examiner-C. Fv Warren Attorney, Agent, orFirm-Plumley & Tyner [57] ABSTRACT Compounds which in the form of thefree acid correspond to the formula n=n N R N -QZ OH (30 H) wherein R Rn,, n, and n have the meaning given in the description. The newdyestuffs dye vegetable and animal fibre materials and are particularlywell suited for dyeing and printing of leather. They show good fastnessproperties, such as eg, resistance to acid, resistance to alkalies,resistance to formaldehyde, resistance to solvents, resistance tofat-liquoring, or dyeability in hard water; in particular the goodfastness to light of the dyestuffs is to be stressed.

4 Claims, N0 Drawings TETRAKISAZO COMPOUNDS wherein n, represents 0, 1,2 or 3 and The subject of the present invention are new azo dyen or 1,stuffs which in the form of the free acid correspond to is diazotised,then coupled onto an aminonaphthol sulthe formula 5 phonic acid of theformula 2 HO N N 0H on N' N N N- I H wherein R represents a halogenatom, a nitro, cyano, sul- 0H KH phonic acid, carboxylic acid, acyl oracylamino group, R hydrogen, halogen, an alkyl, alkoxy or sul- 3 n IIIphonic acid group,

n an integer O, l, 2 or 3, wherein n an integer O or 1 and n;,represents 1 or 2, in that the resulting aminodisazo n an integer l or 2dyestuff is further diazotised and coupled with 1,3- as well as theirproductio and dihydroxy benzene and finally the resulting trisazo dye-As halogen atoms ther may b ti d i ni stuff which in the form of thefree acid corresponds to lar Cl and Br. the formula no N N Q N N N N OHIV I 11) (SO H) Suitable acyl groups R are alkyl carbonyl, alkoxywherein carbonyl and alkyl sulphonyl radicals each with 2 5 11represents 0, l, 2 or 3 C atoms. n 0 or 1 and Suitable alkyl radicals Rare methyl and ethyl radin 1 or 2 cals. combined with a diazotisedaniline of the formula Suitable alkoxy radicals R are methoxy, ethoxy,propoxy and butoxy radicals. 1

Particularly preferred dyestuffs of the formula I are E NH such in whichR represents a nitro group and R hydrogen, methyl, methoxy or SO H.

The new dyestuffs are obtained in that an aminomonoazo dyestuff which inthe form of the free The aminomonoazo dySIUffS Of the formula are d6- idcorresponds to the f l scribed as intermediate or end products, forexample,

in Chem. Ber.2l, 3265 (1888) and the German Pat. specifications 73901,83572, 84460 and 99501 as well 2 Suitable aminonaphthol sulphonic acidsof the formula III are l-amino-8-naphthol-3,6-disulphonic acid,1-amino-8-naphthol-4,6-disulphonic acid and l-amino-8-naphthol-4-sulphonic acid.

Suitable anilines of the formula V are 2-, 3- and 4- (50 10 (SO- ll)nitroaniline, 2-, 3- and 4-chloroaniline. 2-, 3- and 4- 1 2bromoaniline, 2-, 3- and 4-sulfunilic acid, dichloroanilines such ase.g.,- 2,4-dichloroaniline or 2,5 dichloroaniline,2-methoxy-4-nitroaniline, 2-methoxy-5 nitroaniline,2-methyl-4-nitroaniline, 4-carboxyaniline, 4-carboethoxyaniline,4-acetyl-aminoaniline.

The salting out of the dyestuffs can also be carried out by the additionof other customary electrolytes, such as e.g. potassium chloride orsodium sulphate.

EXAMPLE 2 The new dyestuffs dye vegetable and animal fibre 5 materialsolive. are particularly well suited for 1-amino-naph[halene-4-sulphonicacid are dyeing and Printing Ofleathershow good fastness diazotised andcoupled in a weakly acid medium onto properties, such as e.g.,resistance to acid, resistance to 223 g f 1- i n phthalen -6-sulphoniid, Aft alkalies, resistance to formaldehyde, resistance to 501-Completion f couphng h aminoazo d ffi f h Vents, resistance to q gl 0rdyeabihty hard 10 diazotised in a known manner and reacted in the alka-Water; in Particular, t good fastness to light of the line region with31.9 g of 1-amino-8-naphthol-3.6- dyestuff? is to be Stresseddisulphonic acid. The amino-disazo dyestuff is further diazotised andcoupled in the alkaline region onto 1 1.0 EXAMPLE 1 g of 1,3-dihydroxybenzene. Finally, 13.8 g of diazo- 22.3 g f lmin -n p halene-5-su phpnia i ar tised p-nitroaniline are coupled onto this trisazo dyediaz tis din a known mann r a up d in a w akly stuff. The dyestuff whichprecipitates by the addition of Mid medium O g of1-amil10-naPl1thaleI1e-7- sodium chloride is easily soluble in water anddyes cotsulphonic acid. After completion of coupling the ton, butinparticular leather, olive. The dyeings possess aminoazo dyestuff isfurther diazotised in a known good fastness properties, for example,good fastness to manner and reacted in the alkaline region with 31.9 gli ht, of 1-amino-8-naphthol-3,6-disulphonic acid to producel-amino-naphthalene-4'sulphonic acid can also be the diazo dyestuff. Theamino-diazo dyestuff is further replaced, for example, byl-amino-naphthalene-S- diazotised and coupled in the presence of alkalionto sulphonic acid or l amino-8-naphthol-3,o-disulphonic 11.0 g .ofl,3-dihydroxy benzene. Finally, 13.8 g of acid byl-amino-8-naphthol-4,6-disulphonic acid or 1- diazotised p-nitroanilineare allowed to act on this 25 amino-8-naphthol-4-sulphonic acid byl-amino-8- trisazo dyestuff. The dyestuff which precipitates by thenaphthol-2,4-disulphonic acid finally, p-nitroaniline by addition ofsodium chloride is easily soluble in water mor o-nitroaniline orderivatives of these. in every inand dyes cotton, but especiallyleather, olive. The dyestance valuable olive-coloured dyestuffs withonly ings possess good fastness properties. slight differences in shadeare obtained whose dyeings if instead of p-nitroaniline the diazocompounds of on leather are distinguished by good fastness propermoro-nitroaniline or l-amino-2-methoxy-4 or 5- ties, for example, 8fastness to light. nitro-benzene or 1 amino-4-nitro-2-sulphonic acidben- The large number of possible combinations which are zene are used,then dyeings with a similar shade and found when the basic structure ofthe dyestuff is resimilar good fastness properties are obtained. tainedand only the positions of sulpho groups or nitro In some cases it isadvantageous to carry out one or gr up and further SubStiluefllS in the6 mp nen more intermediate isolation steps and/or to purify the Changedmay be Seen from the following Table in which end product byredissolution. y a few examples are given- E R A B c N i:

. l l l 2 I HO N N-- OH I N N N N- OH I I ($0 11) I l l (30 10 1 K I lComponent A Component B Component C Component E Shadel-aminolaminol-amino-B- l-amino-4- olivenaphthalenenaphthalenenaphtholnitro-benzene 4-sulphonic o-sulphunic3.6-disulacid acid phonic acid l-aminol'aminol-amino-8- l-amino-4- olivenaphthalenenaphthalene naphtholnitro-ben- S-sulphonic- 6-sulphonic-3.6-disulzene acid acid phonic acid (ontinucd Component A Component BComponent C Component E Shade l-uminol-amino l-amino 8- l-amino-4 olivenaphthalenenaphlhalenenaphtholnitro-benzene 5-sulphonic o-sulphonic 4,6disulacid acid phonic acid laminol-aminolamino-8- l-amino-4- olivenaphthalenenaphthalene naphtholnitro-benzene 4-sulphonic 7-sulphonic3.6-disulacid acid phonic acid l-aminol-aminol-amino-B- i-amino-S- olivenaphthalenenaphthalene naphtholnitro-benzene 4-sulphonic lS-sulphonic3,6disulacid acid phonic acid l aminol-aminol-amino-S- l-amino-3-brownish naphthalenenaphthalenenaphthol-3,6- nitroolive 4-sulphonic7-sulphonic disulphonic benzene acid acid acid l-aminol'aminol-amino-8-l-amino-4- brownish naphthalenenaphthalenenaphtholnitro-benolive3.6-disulo-sulphonic 3,6-disul- I zene phonic acid acid phonic acidl-aminol-aminol-arnino-8- (i l-amino-4- olivenaphthalenenaphthalenenaphtholnitro-benzene 4-sulpho'nic o-sulphonic4-sulphonic acid acid acid l'amino l-aminol-amino-8- l-amino-4' olivenaphlhalenenaphthalenenaphtholnitro-benzene 4-sulphonic o-suiphonic2,4-disulacid acid phonic acid l-aminol-aminol-amino-8- l-amino-Z- olivenaphthalcnenaphthalenenaphtholmethoxyi- 5-sulphonic -sulphonic3,6-disulnitro-benzene acid acid phonic acid l-aminol-aminol-amino-8-l-amino-4- olive naphthalene naphthalenenaphtholnitro'benzene sulphonic3,6-disul acid phonic acid l-amino' l-aminol-amino-8- l-amino -4- olivenaphthalcnenaphthalene naphtholnitro-bcnzene 3,6-disul- 3,6-disulphonicacid phonic acid l-aminol-aminol-amino-B- l-amino-2- olivenaphthalenenaphthalenenaphtholmethoxy-S 4-sulphonic 7'sulphonic4,6-disulnitro-benzene acid acid phonic acid l-aminol-aminol-amino-S-l-amino3- brownish naphthalenenaphthalenenaphtholnitroolive 4-sulphonic7-sulphonic 4,6-disulbenzene acid acid phonic acid l-amino' l-aminol-amino-B- l-amino-2,4- olive naphthalenenaphthalene' naphtholdichloro-3,6-disnl- -sulphonic 3.6disulbenzene phonic acid acid phonic acidl-aminol-aminol-amino-B- l-amino-3- olivenaphthalcnenaphthalenenaphtolnitro-benzcne 3,6-disul- 6-sulphonic3.6-disulphonic acid acid phonic acid l-aminol-aminol-amino-S-l-amino-2- olive naphthalenenaphthalenenaphthol-3,6- nitro-benzene3,6-disulo-sulphonic disulphonic phonic acid acid acid I claim: I 1.Compound which in the form of the free acid has the formula (SO H)wherein R is nitro and R is hydrogen or methoxy, 2. Compound of theformula 3. Compound of the formula 4. Compound of the formula on on N gOH N N N=N 0 N02 N N N =IN I 130 s f i p MN 0 N92 I 'HO S 50 3 SO H I

2. Compound of the formula
 3. Compound of the formula
 4. Compound of theformula